Paper containing alkyl glycidyl mixed esters and amine reaction products thereof

ABSTRACT

MIXED ALKYL GLYCIDYL ESTERS OF POLYCARBOXYLIC ACID OR ANHYDRIDE-CONTAINING ADDUCTS OF OLEFINICALLY UNSATURATED NATURAL OILS AND OF POLYCARBOXYLIC ACID OR ANHYDRIDE-CONTAINING COPOLYMERS WITH ALPHA-OLEFIN COMPOUNDS, AND AMINE REACTION PRODUCTS THEREOF, WHICH ARE USEFUL IN THE PREPARATION OF SIZED CELLULOSIC PAPER SUBSTRATES AND IN THE PREPARATION OF CURED FILMS AND SOLIDS RESINOUS POTTING COMPOSITIONS.

Patented Feb. 9, 1971 3,562,102 PAPER CONTAINING ALKYL GLYCIDYL MIXEDESTERS AND AMINE REACTION PRODUCTS THEREOF Van R. Gaertner, Ballwin,Mo., assignor to Monsanto Company, St. Louis, Mo., a corporation ofDelaware No Drawing. Original application Dec. 17, 1965, Ser. No.514,709, now Patent No. 3,459,715. Divided and this application Oct. 31,1968, Ser. No. 772,401

Int. Cl. D21h 3/44 US. Cl. 162-168 Claims ABSTRACT OF THE DISCLOSUREMixed alkyl glycidyl esters of polycarboxylic acid oranhydride-containing adducts of olefinically unsaturated natural oilsand of polycarboxylic acid or anhydride-containing copolymers withalpha-olefin compounds, and amine reaction products thereof, which areuseful in the preparation of sized cellulosic paper substrates and inthe preparation of cured films and solid resinous potting compositions.

This application is a division of application Ser. No. 514.709, filedDec. 17, 1965, now Pat. No. 3,459,715.

This invention relates to glycidyl esters of modified natural oils, topartial esters of synthetic polymers, and to uses of the resultingproducts in the making of films and in the making of water dispersible,polyamide derivatives which are especially suited for use as a cellulosesizing agent, e.g., paper or textile sizing agents. More particularly,this invention provides mixed alkyl glycidyl esters of reaction productsof maleic anhydride and natural and synthetic olefinic materials. Italso provides useful film forming amine reaction products of said alkylglycidyl esters, as well as water dispersible quaternary aminederivatives of said alkyl glycidyl esters.

An object of this invention is to provide economically obtainableversatile mixed poly(alkyl glycidyl esters) which are adaptable for usein widely varying circumstances, such as in the making of cured filmsand solid resinous potting compositions, and in the making of Waterdispersible, substantive paper and textile sizing agents.

A further object of this invention is to provide water dispersible aminecontaining derivatives of the mixed alkyl glycidyl esters.

A further object of this invention is to provide a sizing compositionfor paper which allows facile broke recovery by the sized papermanufacture.

A further object of this invention is to provide a method for preparingmixed alkyl glycidyl esters of polycarboxylic acid or anhydridecontaining adducts of olefinically unsaturated natural oils and ofpolycarboxylic acid or anhydride containing synthetic polymers withalphaolefin compounds.

Briefly, this invention provides a process for preparing new mixed alkylglycidyl esters of (a) adducts of maleic anhydride and a non-conjugated,olefinically unsaturated, non-hydroxylated, fatty oil having an averageof from 10 to 24 carbon atoms in the carbon chain of the fatty acidmoiety of said fatty oil, and (b) a polymer of maleic anhydride and apolymerizable alpha-olefin, by reacting an epihalohydrin with a carboxylcontaining lower alkyl partial ester of the reaction product (a), or (b)above in the presence of a quaternary ammonium catalytic compoundcatalyst, and an alkali metal salt forming basic compound. Theepihalohydrin is used in excess to drive the reaction toward formationof a poly (alkyl glycidyl) mixed ester product. The alkali metal saltforming basic compound is preferably a sodium or potassium loweralkoxide dissolved in excess alcohol and is used in an amount which isabout stoichiometrically equivalent to the degree of reaction desired bythe epihalohydrin and the partial ester reaction product. In addition,this invention contemplates using the poly(alkyl glycidyl) mixed esterreaction products as intermediates, for making cross-linked or curedsolid resinous polymers which can be used in making films and as solidpotting compositions by treating the product with aliphatic poly-primaryamines, but more particularly, as intermediates in the preparation ofWaterdispersible sizing agents for paper and cellulose containingtextiles by reacting the mixed alkyl polyglycidyl ester reaction productwith a diamine having at least one secondary or tertiary amino group, inthe presence of a diluent mixture of a hydroxyl containing organiccompound and water, at a temperature of from about 20 C. to C.

The resulting amine treated solutoins may be used as such as a wet endor internal size by applying it to the pulp slurry used to make paper oras a surface size by application to a paper web. When the amine treatedproduct is not to be used for some time it is preferred to stabilize itagainst substantial cross-linking by treating the amine product with anacid to lower the pH of the product to a stable range, which is usuallybelow pH 7.

As can be seen from the above brief description the mixed alkyl glycidylesters can be prepared from the two different types of maleic anhydridereaction product starting materials. The preferred reaction productstarting materials are the synthetic polymers of maleic anhydride and analphaolefin because they give better looking products and betterperformance results. However, the maleic anhydride-unsaturated fatty oiladducts may also be used to make effective products according to thisinvention.

The fatty oils which are used to prepare the reaction products of type(a), described above, have been described in detail in the prior artliterature, especially the patent literature. The unsaturated fatty oilsmay be found in the glyceride esterified for more in the free acid form.A few examples of such useful oils are olive oil, peanut oil, almond,neats foot, pecan nut, lard, tung oil, safilower oil, linseed oil,cottonseed oil, soybean oil, etc.

As indicated above, maleic anhydride is preferred for preparing thepolycarboxylic acid or anhydride adduct with the naturail oil. However,other alpha,beta-olefinical- 1y unsaturated polycarboxylic acid oranhydride may be used to replace a part or all of the maleic anhydride,if desired. A few examples of such materials include fumaric acid,aconitic acid anhydride, itaconic acid anhydride, citraconic acidanhydride, mesaconic acid anhydride, half methyl maleate, dimethylmaleate, and compounds which yield maleic anhydride and the like such asmalic acid, maleic acid, citric acid, if subjected to the conditionsunder which maleic anhydride is produced.

For preparing starting materials of type (b) above, maleic anhydride isreacted with polymerizable alphaolefin. The term alpha-olefin and olefinare used herein as general terms to designate olefinically unsaturatedcompounds in which the double bond is in the alpha position, and isintended to include not only olefinically unsaturated branched andstraight chained hydrocarbons such as the aliphatic olefins, e.g.,ethylene, propylene, lbutylene, isobutylene, l-pentylene, l-hexene,l-octene, 1- nonene, l-decene, l-dodecene, l-tridecene, l-tetradecene,l-pentadecene, l-hexadecene, l-octadecene, l-eicosene, ldocosene,l-tetracosene, 1pentacosene, etc. and the aromatic alpha-olefinhydrocarbons such as styrene, alkylsubstituted styrenes such as vinyltoluene, the vinyl xylenes, vinyl 4-ethylbenzene, the chloro-substitutedstyrenes, etc. but is also intended to include other alpha-olefinicallyunsaturated polymerizable compounds such as alkyl vinyl ethers havingabout 8 or more carbon atoms in the alkyl groups, the correspondingalkenyl vinyl ethers having at least about 8 carbon atoms in the alkenylgroup where sizing action is being sought. When it is desired to impartsome wet or dry strength to the paper made from pulp treated with thesepolymeric poly(methyl glycidyl-amine) reaction product compositions thealpha-olefin used may also include the shorter chained olefinichydrocarbons, alkyl vinyl ethers, as well as unsaturated acid monomerssuch as acrylic acid and methacrylic acid, vinyl esters such as thevinyl alkanoates including vinyl acetate, vinyl propionate, etc., theacrylate and methacrylate esters, such as methyl methacrylate, ethylacrylate, and vinyl compounds such as vinyl chloride, vinylidenechloride, etc. Mixtures of the alpha-olefins may be used to react withthe maleic anhydride to make the copolymer materials used for thisinvention, e.g., mixtures of alkyl vinyl ethers and vinyl toluene may bereacted with maleic anhydride to prepare useful copolymers. Thus theterm copolymers as used herein includes the use of interpolymers of morethan two monomer materials.

The alpha-olefins used in preparing the copolymers can vary considerablyin molecular weight and can contain an average of from 2 to about 40carbon atoms. The hydrocarbon alpha-olefins can be obtained fromnaturally occurring compounds or by the polymerization or cracking ofpetroleum fractions and the like. In commercial practice, they aregenerally mixtures containing compounds of varying length. Therefore,the number of carbon atoms attributed to such mixtures represents aweighted average rather than an absolute value. Those copolymersprepared from the lower olefins (say, up to about 12 carbon atoms)result in the formation of products which provide improved wet and drystrength, whereas utilization of the higher olefins provides hard sizingin addition to the other advantageous properties.

Vinyl ethers, which may be used in preparing the copolymers used toprepare the polymeric reaction products, may be prepared in conventionalmanner by treating an alcohol with an alkali catalyst followed byreaction with acetylene. The alcohols used can be straight or branchedchained, obtained from natural products or by synthetically made, e.g.,those alcohols resulting from the x0 and other processes. The vinylethers have the general formula Z-OCH=CH wherein Z is alkyl, alkenyl,aryl, alkoxyalkyl, aryloxyalkyl, alkylaryl and the like containing from2 to about 40 carbon atoms and preferably from about 8 to about 32carbon atoms if hard sizing is desired. Representative vinyl ethers suchas the oxo-decyl, oxo-tridecyl, oxo-hexadecyl, oxo-nonadecyl, propyl,hexyl, n-decy], n-dodecyl, n-octadecyl, n-tetracoxyl, n-tritriacontyl,tetratricontyl, n-hexatriacontyl vinyl ethers, the corresponding alkenylvinyl ethers, a few examples of which are dodecenyl vinyl ether,heptadecenyl vinyl ether and octadecenyl vinyl ether, as well as thearyl, aralkyl, and alkaryl, alkoxyaryl, aryloxyaryl, aryloxyalkyl vinylethers, e.g., pheynl, benzyl, tolyl, xylyl, dodecylphenyl,octadecylphenyl, dinonylphenyl, methoxyphenyl, ethoxyphenyl,dodecyloxyphenyl, octadecyloxyphenyl, phenoxyhexyl, phenoxyoctyl,phenoxyoctadecyl vinyl ethers and the like.

The alpha-olefin-maleic anhydride copolymers utilized as startingmaterials in the preparation of the polymeric alkyl glycidyl estersusually contains essentially equimolar proportions of the alpha-olefinand maleic anhydride units. However, copolymers in which the molar ratioof maleic anhydride to alpha-olefin is from about 0.90:1 to about 1.8:1can be utilized. Copolymers having about equimolar amounts of maleicanhydride are preferred. The best sizes are made from copolymers havingsubstantially alternating maleic anhydride-olefin moieties. Thecopolymers are prepared in conventional manner with or without solventssuch as benzene or xylene, and using catalysts such asazobis(isobutyronitrile), di-t-butyl peroxide, tbutyl perbenzoate,benzoyl peroxide, and any initiator which will be effective at fromabout SO'ISO" C. such as isopropyl peroxydicarbonate, tetrachlorobenzoylperoxide and the like. The polymers employed in accordance with thisinvention have molecular weights of at least about 2,000, and may rangeup to the general neighborhood of about 200,000. Molecules of excessivesize introduce operational difliculties such as a rapidly increasingtendency to gel, reduced ease of application and the like; whereaspolymers having a molecular weight substantially under 2,000 provideless satisfactory sizes. However, it is considered that the bettercopolymers used in this work preferably have an average molecular weightsubstantially under 2,000 provide less satisfactory sizes. However, itis considered that the better copolymers used in this work preferablyhave an average molecular weight of from about 50,000 to about 115,000.Copolymers having these molecular weights are generally those made bypolymerizing one or more alkyl vinyl ethers with maleic anhydride.

The epihalohydrin reactant used in the process of this invention ispreferably epichlorohydrin but may be epibromohydrin, epiiodohydrin, orother vicinal halohydrins such as 1,2 epoxy 3 chlorobutane,1,2-epoxyl-bromopentane,etc.

Before reacting the reaction product (a) or (b) above with theepihalohydrin, it is treated with a suitable alcohol under conditionswhich cause ring opening of the maleic anhydride moieties in the adducts(a) or polymers (b) and esterification of one of resulting carboxylgroups. It is preferred that such alcohol be a lower alkanol such asmethanol, ethanol, propanol, or a small alkoxyalkanol such asmethoxyethanol, butoxyethanol, etc. Heating a mixture of the maleicanhydride fatty oil adduct (a) or the maleic anhydride-alpha-olefincopolymer and the alkanol to reflux until the anhydride content issubstantially depleted is sufiicient for preparing the starting materialfor this invention. A tertiary amine catalyst such as triethylaminegreatly speeds the esterification. It is preferred to reduce theanhydride content to less than one percent of the original anhydridecontent of the adduct or polymer for etficient use of chemicals.

In conducting the process of this invention the maleic anhydride fattyoil adduct (a) or the maleic anhydride copolymer (b) is mixed with atleast a stoichiometric amount of the epihalohydrin relative to thecarboxyl content of the partially esterified starting material in awater diluted solution of an appropriate organic solvent, e.g., analkanol such as butanol, or a hydrocarbonalcohol mixture such as anisopropanol xylene mixture, butanol-toluene and the like, but ispreferably a water diluted excess of the epihalohydrin so that theexcess serves as a diluent or solvent for the reacting materials. TheWater should constitute from about 20 percent to 50 percent of the totalsolvent system used, and is preferably within the range of from about 30percent to 40 percent of the solvent. To accomplish esterification inany reasonable period of time a quaternary ammonium basic compound isadded as catalyst for the addition of the epihalohydrin to the freecarboxyl group on the maleic moiety. Examples of quaternary ammoniumcompounds which may be used are long chained alkyland aralkyltris-loweralkyl ammonium hydroxide and salts, e.g., hexadccyltrimethylammoniumchloride, octadccyltriethylammonium bromide, benzyltrimethylammoniumhydroxide, tetraethylamrnonium chloride and(4-methylbenzyl)trimethylammonium sulfate, etc.

In addition to an excess of epihalohydrin, and the use of a quaternaryammonium compound catalyst, there is used in this step of the process analkali metal salt forming basic compound which is used in an amount atleast stoichiometrically equivalent to the amount of free carboxylcontent of the starting partially esterified adduct (a) or polymer (b)which liquid phases, and drying of the product over suitable agents suchas sodium sulfate and magnesium sulfate, etc.

These resulting products which contain mixctl alkyl glycidyl esters ofthe adduct (a) or polymer (b) starting materials contain numerousgroups, and are not to be confused with products prepared from anepihalohydrin so as to contain only hydroxyalkyl ester groups, e.g.

These intermediate products of this invention may be reacted withvarious known epoxide cross-linking agents such as the aliphaticpoly-primary amine alkylene polyamines, and polyalkylenepolyamines,having from 2 to 4 carbon atoms in the hydrocarbon moieties between thenitrogen atoms, e.g., ethylene diamine, diethylene triamine,dipropylenetriamine, tetraethylenepentamine, tributylenetetramine, etc.as well as with polycarboxylic acids and anhydrides thereof to formcured films and solid resinous bodies such as are used in waterimpervious coatings for cellulosic materials, as well as pottingcompositions used in encasing manufactured electrical devices, but theyare particularly suited for use as intermediates in the manufacture ofwater dispersible sizing agents for cellulose containing materials suchas paper, paper board and cellulose containing textiles.

Although the poly(methyl glycidyl) mixed ester product of the adduct(21) or the polymer (b) can be reacted with enough amine in the presenceof an hydroxyl con taining material to react with all of the glycidylgroups of the intermediate product, it is not necessary to so react allof the glycidyl groups. In general, the numerical ratio of epoxide orglycidyl groups to quaternary amine groups in the amine treated productcan vary between about :1 and 2:1. It is preferred to maintain thisratio between about 0.1 :1 and about 1.5 1. An increased ratio of water:solvent favors higher quaternary contents, thus better aqueoussolubility.

The reaction between the poly(alkyl glycidyl mixed ester) intermediateand the diamine reactant can be conveniently carried out at moderatetemperatures of from 0 C. to about 50 C., but preferably at 35 C. byadding an appropriate amount of the amine to an aqueous solution of thepoly(alkyl glycidyl mixed ester) intermediate in the presence of adiluent or solvent system which is an Organic hydroxyl containingcompound or compounds which are volatilizable at temperatures below 100C. at atmospheric pressure, which is preferably an alcohol such asmethanol, Z-propanol, butanol, ethoxyethanol, butoxyethanol,butylcarbitol, methanol-xylene mixtures, isopropanol-toluene mixtures,or which may be any other hydroxyl compound such as phenol, alkyleneglycols, etc. The organic hydroxyl containing compound solvent used forthis amination step may also contain some Water if desired, but usuallyis not more than 50 percent of the total solvent system used. Preferablythe water is used in amounts of from 1.0 to percent of the total solventsystem used in this step. Since the reaction is not instantaneous, theamount of amine entering the reaction can be controlled by the reactiontime and temperature as well as by the amine added to the mixture.Although the reaction progresses slowly in the absence of appreciablewater, it is catalyzed and proceeds quite rapidly upon the addition ofthe stated quantities of water. When water is added, the resultingaqueous mixture originally may become turbid. The turbidity of theaqueous reaction mixture may usually be dissipated, if desired,

by dissolving the reaction product in aqueous mixtures of 2-propanol,e.g., a 2:1 volume water:2-propanol mixture. The resulting solution canthen be diluted with additional Water to any desired concentration foruse as sizing agents.

The resulting amine treated poly(alkyl glycidyl mixed ester) productshave a relatively short shelf or storage life since they are subject tocross-linking and gelation. In order to stabilize them in a convenient,commercially available form they are preferably treated with ahydrohalic acid, especially when some unreacted glycidyl groups arepresent in the amine treated product to adjust the pH thereof to betweenabout pH 5 and pH 7, preferably pH 6 to 7. The hydrohalic acid, e.g.,hydrochloric acid, or hydrobromic acid may be added alone, or incombination with other mineral acids such as phosphoric, sulfuric andthe like. When the product contains no free glycidyl groups it may bestabilized with a mineral acid composition containing no hydrohalicacids. Such stabilizing compositions neutralize amino groups present,but do not add to any epoxides. Other inorganic and organic acids couldalso be used to effect stabilization of the product but the abovementioned acids are the most economical. The acid treatment converts thesecondary amino or tertiary amino groups of the product to correspondingless reactive amine salt form which essentially stops further reactionor polymerization. These acidified amine treated poly(alkyl glycidylmixed ester) products are stable for long periods of time, and thus canbe subjected to normal shipping and storage without any danger ofcross-linkage or consequent gelation.

With the acid stabilized amine treated products derived from poly(alkylglycidyl mixed esters) of the maleic anhydride-fatty oil adducts (a) andthe hydrocarbon alphaolefin maleic anhydride copolymers (b), it isgenerally desirable to pretreat them with an alkaline material, i.e., abase such as an alkali metal hydroxide to put them in a chemical formmost suitable to efliciently size the cellulose pulp or paper. Similaracid stabilized products prepared from the alkyl vinyl ether/maleicanhydride copolymers, do not generally require such pre-treatment with abase before application to the pulp slurry or paper web. Thisalternative is of great benefit to the paper-maker users of thesereaction products in that these products obviate any necessity forexpensive machinery to pre-treat the chemical size compositions beforeapplication to the pulp.

Using the partial methyl ester of an alpha-olefin hydrocarbon/maleicanhydride copolymer as an illustrative starting material, theintermediate poly(methyl glycidyl) mixed ester product (I) is believedto have essentially alternating polymeric units of the following typetherein where n is a positive whole number of from 0 to about 40,denoting an alkyl group, and x and y are numbers greater than 0, thepreferred ratio of y to x being at least about 0.9:].

The amine treated poly(methyl glycidyl) mixed ester products (II) can beexemplified by a product of the type described above treated with, forexample, a ditertiary alkylene diamine such asN,N,NN'-tetramethylethylenediamine to obtain a product having randomlyrecurring units of the following types; the olefin-derived unitsalternate with various anhydride-derived units.

where x, y, z and s are whole numbers of greater than 0.

Upon treatment of the resulting product with an acid, preferablyhydrochloric acid to adjust the pH of the composition to within therange of from about to 7, and preferably to within pH 6 to pH 7, thesame product can have the following randomly recurring anhydride derivedgroups:

in addition to the alpha-olefin monomer units. Care should be taken toavoid adding too much acid during stabilization to reduce the pH of thecomposition to much below the stated lower limit to avoid hydrolysis ofthe ester groups until use. Similarly, pH conditions much above about pH10 are to be avoided even during brief pretreatment of the amine productII to avoid hydrolysis of the ester groups in the product. However, oneof the advantages of the products of this invention is that after havingbeen applied to paper, cured and dried to obtain a good sized paper, thewaste paper resulting from trim ming, and the recovered machine broke"obtained after the sizing operation can be treated with either acid oralkali to hydrolyze ester groups of the size composition to assist inthe recovery and reuse of the waste pulp to form additional paper. Theinvention is further illustrated by the following detailed examples.

EXAMPLE 1 A 40 g. portion of a copolymer of a (E -C mixed alkenylalpha-olefin hydrocarbon and maleic anhydride present in a mole ratio of1:11 of olefinzmaleic anhydride was treated with 80 g. of methanol,sealed in a bottle and rotated in an oven at 60 C. overnight, and thenfor three days.

A 61 g. portion of this methanol-polymer solution, containing 0.068anhydride mole equivalent was mixed with 92.5 g. (1.0 mole) ofepichloroliydrin, and 3.4 g.

of a 40% aqueous solution of the quaternary bcnzyltrimethylammoniumhydroxide, at once, and then with 15.0 ml. (0.06 mole) of a 4.42 Nsolution of sodium rnethoxide in methanol, dropwise, at 95 C. whiledistilling methanol and water into a phase-separating distillation head,While stirring the mixture.

When 77 ml. of the distillate had collected, the distillation head wasdrained, and the trap was filled with epichlorohydrin, while continuingto heat the mixture to C. (pot temperature) for 1 hour to insurecomplete reaction.

After allowing the pot residue to cool overnight it was filtered, rinsedwith epichlorohydrin and the resulting clear amber solution wasdistilled to remove epichlorohydrin to 110 C./10 mm. leaving 28.0 g. ofa translucent light cream colored gum, which was free flowing at 110 C.,and which barely flowed at 25 C. The oxirane content of thispo1y(glycidyl methyl C C mixed olefin/maleate succinate) was 3.18%, ascompared to a theory of 4.37% following the analytical procedure adaptedfrom that of A. J. Durbetaki, Anal. Chem., 28, 2000 (1956). The polymerhad a specific viscosity (4% by weight) of 0.33 in methyl ethyl ketone.

EXAMPLE 2 A 2.0 g. portion of the polyester, prepared as described inExample 1, was dissolved in 2.0 g. of butoxyethancl with warming andthen at 32 C. was treated dropwise with 0.3 g. (4 meq.) ofN,N,N,N'-tetramethyl-1,3- butanediamine and with 10 drops of water at 31C. to cause turbidity. The mixture was stirred until the turbiditycleared in 10 minutes. An additional 10 drops of Water was added whileheating the mixture to from 29 C. to 32 C. for 1 hour. The mixturebecame homogeneous when it was heated to about 40 C, An additional 10drops of water was added while heating the mixture to 60 C. On standingovernight the poly(glycidyl methyl Guy-C1 mixed alkenyl/succinate:1,3-butylenebisdimethylene) copolymer set to a soft rubbery gel.

EXAMPLE 3 A 21.4 g. portion of the poly(glycidyl methyl) C C mixedalkenyl/maleate copolymer prepared as described in Example 1 wasdissolved in 20.0 g. of butoxyethanol with warming, and then treatedwith 2.3 g. (0.02 mole) of N,N,N',N-tetramethylethylenediamine at once,at 25 C. with stirring. The temperature rose to 28 C. and then droppedto 27 C. Then 10 g. of solution containing 1.42 g. of HCl as 4.0 g. of a37% aqueous solution was added over 3.67 hours at 28-40 C. with stirringto maintain the turbid mixture at a pH of 45. After stirring the mixtureovernight, the viscous product was treated with 4.0 g. of concentratedhydrochloric acid and 30.0 ml. of methanol. The gummy reaction productwas mixed with butoxyethanol and then with water to give a water solublesolution of poly(glycidy1 methyl. C C mixed alkenyl/maleatc):N,N,N',N'tetramethylethylenediamine atlduct.

EXAMPLE 4 A 164 g. portion containing 0.5 maleic anhydride equi valents)of an alphacctadecene/maleic anhydride copolymer, having an octadeceneto maleic anhydride molar ratio of 1:1.1, and a specific viscosity (4%)of 0.35, was treated with 200 g. of methanol while stirring and heatingat reflux for 18 hours to form the halfmethyl ester of the maleicmoieties of the copolymer. After removing 50 ml. of methanol from theoily but homogeneous reaction product, the hot solution was cooled to amilky solution.

A g. portion of the resulting poly(methyl half-ester of theoctadecene/maleic) copolymer in methanol was treated with 231 g. (2.5moles) of epichlorohydrin and with 10.5 g. of an 40% aqueous solution ofthe quaternary benzyltrimethylammonium hydroxide. The mixture was heatedto 117 C. to distill methanol. and then 565 ml. of a 4.42 N sodiummctlioxide in methanol solution was added slowly and the mixture washeated at 117- 120 C. for 75 minutes, stirred and refluxed. Theresulting mixture which had a pH of less than 8 was allowed to standovernight and then 200 ml. of distilled water was added. Upon stirring,the turbidity of the mixture cleared. A sodium sulfate solution wasadded to speed separation of the aqueous layer from the epichlorohydrinlayer. The epichlorohydrin layer, containing the product, was separatedand dried over sodium sulfate. After filtering, the amber fluid solutionwas aspirated to 125 C./l mm. to leave as residue 105.7 g. of lightamber, clear poly- (glycidyl methyl octadecene/maleate) having aspecific viscosity of 0.32 (4% of polymer in methyl ethyl ketone) and anepoxy equivalent of 447.

EXAMPLE 5 A g. portion of the poly(glycidyl methyl octadecene/maleate)polymer, prepared as described in Example 4, and containing 56milliequivalents (me) of glycidyl groups, was dissolved in 25.0 g. ofbutoxyethanol by warming. After cooling, the resulting solution wastreated with 3.6 g. (50 me.) of N,N,N',N' tetramethyl 1,3-butanediamine. While stirring the mixture, water addition was begun at26 C. and continued over 185 minutes until 20 ml. of H 0 had been added.The temperature rose to a maximum of 42 C. during this time. Afterstirring an additional 85 minutes to insure complete reaction, there wasadded at 42 C. 10 ml. of solution containing 5.0 g. (50 millimoles) ofcone. hydrochloric acid. An additional 10 m1. of the acid solution wasadded after minutes. The reaction mixture was water dispersible. Afteradding 50 g. of butoxyethanol and then 33 g. of water the resultingtranslucent solution was clear. It was diluted with Water to 19.4%polymer solids and used to size paper by immersing the paper in thesolution. The resulting poly(glycidyl methyl octadecene/maleate) :N,N,-N',N'-tetramethyl-1,3-butanediamine product had a specific viscosity of0.15 (1% in water at pH of 4).

EXAMPLE 6 A 53 g. portion of a 1:1.1 molar ratio styrene/maleicanhydride copolymer was mixed in 200 g. of methanol and mixture washeated to reflux (65 C.) with stirring until infrared analysis ofsamples indicated that no anhydride absorption remained and that onlythe half methyl ester was present.

After distilling the mixture to remove 170 ml. of methanol from thestyrene/maleic half methyl ester copolymer, 231 g. (2.5 moles) ofepichlorohydrin and 10.5 g. (0.025 mole) of aqueousbenzyltrimethylammonium hydroxide was added. The resulting mixturebecame homogeneous, was stirred and distilled to remove methanol and toremove an azeotrope of water with epichlorohydrin to a pot temperatureof 120 C. Then the addition of 56 ml. of 4.4 N sodium methoxide inmethanol solution was commenced dropwise and continued for 1 hour whiledistilling methanol to 100 C. Heating to 117 C. and stirring werecontinued for 1 hour to insure complete reaction, leaving a viscoussolution of poly(glycidyl methyl styrene /maleate).

EXAMPLE 7 A 2.24 g. (5 me.) portion of the poly(glycidyl methyloctadecene/maleate) polymer, prepared as described in Example 6, wasmixed thoroughly with 1.03 g. (5 me.) of diethylenetriamine. Theresulting mixture was warmed to 60 C. in an oven. After minutes theresulting polymer mixture set to a hard, friable cross-linked solid.

EXAMPLE 8 A copolymer of l-hexene and maleic anhydride was prepared bycombining 367 g. (3.75 moles) of maleic anhydride and 342 ml. (4.06moles) of l-hexene in 750 ml. of ethyl acetate using 21.25 g. of2,2-azobis[2-methylpropionitrile] as catalyst, and heating at 70 C. to75.5 C. to reflux the mixture. Methanol was added to precipitate thel-hexene/maleic anhydride copolymer. After drying there was obtained 507g. of copolymer (71.5% yield) which had a specific viscosity of 0.09 (1%in methyl ethyl ketone).

To a mixture of 600 g. of methanol and 0.5 g. of triethylamine, warmedto C., a 200 g. portion of the l-hexene/maleic anhydride copolymer,prepared as described above, Was added so as to prevent the copolymerfrom balling up. The mixture was heated to reflux (64- 65 C.). Wheninfrared analysis showed that only traces of anhydride groups remainedin the polymer, i.e., the half methyl ester of the maleic moieties hadformed, there was added 925 g. of epichlorohydrin while slowlydistilling methanol. A 20.9 g. portion of a 40% (0.05 mole) solution ofbenzyltrimethylammonium hydroxide in water was added as the temperaturewas maintained below 110 C., while providing for the removal of methanolfrom the distillation trap. Then 223 ml. (1000 me.) of sodium methoxidein methanol solution was added over minutes at -110 C. and then thetemperature was raised and held at l15-l18 C. A total of 572 g. ofepichlorohydrin was distilled out of the mixture with methanol. Anadditional 500 g. of epichlorohydrin was added and the reaction mixturewas heated at 1l5120 C. for 2 hours.

l The mixture was cooled to 4050 C and 200 cc. of

water was added. After mixing thoroughly, the contents were separatedinto an aqueous layer and an organic layer, diluted with chloroform.After drying the chloroform diluted portion, the liquid was placed in aflask and distilled in partial vacuum to remove chloroform andepichlorohydrin at temperatures below 100 C. distillation was continueduntil a temperature of C./4 mm. was reached. The resulting product,poly(glycidyl methyl 1- hexene/maleate) had an epoxide oxygen content of4.82% as compared with a theoretical epoxide content of 5.94%.

EXAMPLE 9 To a reaction vessel fitted with a stirrer, condenser,addition funnel, and nitrogen inlet there was added 362 g. (0.3 mole) ofsafflower oil, containing 73% linoleic acid. 21% oleic acid, and 6%saturated fatty acids. The vessel was swept with nitrogen to remove airtherefrom. The safilower oil was heated to 200 C. and then there wasslowly added thereto 88.2 g. of molten maleic anhydride (0.9 mole) over2 hours. The temperature was raised to 220 C. until all of the maleicanhydride had reacted and then the reaction mixture was stripped oftrace volatile material to 220 C./2 mm.

A 343.7 g. portion of the resulting safllower oil-maleic anhydrideadduct was mixed with 200 g. of methanol and refluxed until the reactionto form the half methyl ester was essentially completed. Excess methanolwas distilled off under vacuum and then 322 g. (3.48 moles) ofepichlorohydrin (carboxy:epichlorohydrin 1:5) was added and mixedthoroughly. Then 29.2 g. of 40% benzyltrimethyl ammonium hydroxide inwater solution was added. Then 156 ml. (700 me.) of sodium methoxide inmethanol solution was added dropwise at a temperature sufficient tofractionate off methanol at a pot temperature of 90 C. The temperaturewas raised very slowly to 200 C. after all of the sodium methoxide hadbeen added and held at that temperature for 2.5 hours. The triglycidyltrimethyl safilower oil-trimaleate product was washed with 200 ml. ofwater, separated, and dried over magnesium sulfate. It weighed 427.0 g.and contained 1.74% oxirane oxygen as compared with a theory of 2.72%oxirane oxygen (64% of theory).

EXAMPLE 10 A mixture of 362 g. of safflower oil (0.30 mole) and 167 g.(1.80 mole) of maleic anhydride was warmed to 200 to 220 C. undernitrogen until no unreacted maleic anhydride was present (infraredanalysis).

A 308.5 g. portion of the resulting 1:6 molar safflower oil-maleicanhydride adduct was treated with 200 g. of methanol, and maintained at60 C. until substantially all 11 anhydride groups had been esterified tothe half methyl ester. Methanol was removed under aspirator vacuum to 80C. Then 1000 g. (10.8 moles) of epichlorohydrin and 41.7 g. of 40%aqueous benzyltriammoniurn hydroxide were added: and 25 ml. of waterfrom the quaternary base was distilled as the azeotrope. After standingovernight the reaction mixture was treated with 223 ml. of 4.48 N sodiummethoxide in methanol solution at a pot temperature of 90l05 C. Methanoland some epichlorohydrin were distilled to a reaction temperature of 117C. and maintained for 2.5 hours. Distillation in vacuo gave a residualproduct containing 2.94% oxirane oxygen (71.3% of theory) forhexaglycidyl hexamethyl safliower oil-hexamaleate (theory, 4.13% oxiraneoxygen).

EXAMPLE 11 The procedure of Example was repeated using 10 molarequivalents of maleic anhydride per molar equivalent of safilower oil.The resulting saffiower oil-maleic anhydride adduct was heated withmethanol to form the half methyl ester of the maleic moieties thereof,and then treated with 690 g. epichlorohydrin usingbenzyltrimethylammonium hydroxide and sodium methoxide in methanol ascatalyst. After washing the crude product with water and then withether, filtering, and removing excess epichlorohydrin and solvent, therewas obtained 299 g. of a poly(glycidylmethyl) saifiower oil-maleateproduct containing 3.09% oxirane oxygen which is 59.3% of theory foroxirane oxygen (5.22% for a decaglycidyl decamethyl saflioweroil-decamaleate product.

EXAMPLE 12 To a solution of the hexaglycidyl hexamethyl safiioweroil-hexamaleate, (50 meq. of epoxide), prepared as described in Example10, in 250 g. of butoxyethanol there was added 2.04 g. of3-(dimethylamin0)propylamine in 10.0 g. of water. Five ml. portions ofwater were added as the mixture was stirred for 27.75 hours. A 2.00 g.of cone. hydrochloric acid in 7 ml. of water was added. The total wateradded was 30 g. The reaction mixture was diluted with 80 ml. ofbutoxyethanol and ml. of water to form a clear 17.0% solids solution ofthe N,N-dimethylaminopropyl amine derivative of the hexaglycidylhexamethyl safflower oil hexamaleate which was stable at pH 6. At pH 4.0and at a concentration of 1% in water this product had a specificviscosity of 0.15.

EXAMPLE 13 A l-decene/maleic anhydride copolymer was prepared bytreating 421 g. (3.0 moles) of l-decene with 323.4 g. (3.30 moles) ofmaleic anhydride using 8.77 g. (0.06 mole) of di-tert-butyl peroxide ascatalyst at a temperature of 145-148 C. The reaction mixture was 165170for minutes after adding the anhydride. After cooling overnight, theresulting l-decene/maleic anhydride copolymer had a viscosity of 0.36(4% solution of the polymer in methyl ethyl ketone.

A 169.5 g. portion of the above l-decene/maleic anhydride copolymer wasconverted to the l-decene/maleic half methyl ester half acid polymer bytreating it with 150 g. of methanol using 0.5 g. of triethylamine ascatalyst at 60 C. while agitating the mixture.

After removing excess methanol there was added 925 g. of epichlorohydrinand 20.8 g. of 40% benzyltrimethylammonium methoxide in methanol. Thenat a pot temperature of 90 C. (head temperature 70-78 C.) there wasadded 229 ml. of 25% sodium methoxide in methanol solution. The methanoldistilled as addition proceeded. When the addition was completed, thetemperature was raised to llS1l7 C. for 4 hours.

A portion of the resulting product was washed with water, and then withether, dried over sodium sulfate, filtered, and distilled to removeether, epichlorohydrin, etc. at 70 C. under aspirator vacuum. Theproduct containcd 5.17% of oxirane oxygen (98% of theory),

EXAMPLE 14 This example illustrates the usefulness of the compositionsof this invention to form a film. For this exatnple the poly(glycidylmethyl l-hexene maleate) polymer, prepared as described in Example 8,was used.

Two solutions of the polymer were prepared, in xylene and 50% inacetone, and cured by adding to the polymer solution diethylenctriamine(DETA) and methyl nadic anhydride (MNA) plus a catalyst, about 0.5% ofN,N-dimethylaniline. The solutions were drawn into a film on tin foil,and allowed to air dry 16 hours at room temperature to remove thesolvents. This was followed by a 1 hour cure at C. The film was re movedfrom the tin foil using mercury as a solvent for the tin. The resultingfilms were 0.0015 inch thick.

The films were then tested to determine the modulus of elasticity,tensile strength and elongation. The following data resulted.

Elongation, DETA I MNA K E 2 ST 3 percent.

Solvent:

Acetone 6 4 2. 56 2,250 1.10 Xylene 0.4 1. 88 3, 00 2. 0 Acetone 54 1.(it) 50!) 0. 4 Xylc|te 54 1.52 2,010 2.15

1 Parts per 101) of the polymer. 2 Modulus oi elasticity X10 p.s.i. 3Tensile strength, psi.

EXAMPLE 15 Samples of the tertiary amine treated po1y(glycidyl methylalkenyl/maleate polymers, prepared as described in the above exampleswere tested for their effectiveness as wet end" sizing agents for paper,i.e., applied to the aqueous pulp slurry used to make the paper.

For this test an aqueous slurry containing 2% Bleached Gatineau Sulfitepulp refined to a Canadian Standard Freeness (CSF) of 507 was mixed withthe following samples, each diluted with 300 ml. of water. Some sampleswere pretreated with base to raise the pH thereof to 9 or 10 todetermine any difference in effectiveness.

Pretreatment None pH 9 pH 10 None pH 9 pH 10 Sample:

A) Example 3-1l.40 g

(B) Example 54.73 g

Penetration,

seconds lttodiinnl Pretreatpcnosuopc, intuit, pll Tnk 11 0 inchesSttmplt A None 2, 650 13 0 2, 850 14 n1 2, 500 1,150 21. 5

B None 1, 012 75 0. 5 SI l, 075 1120 10. 5 10 l, 225 101) 13. 5

Contrnl 7 0 0 l 'i 1 3 EXAMPLE 16 One mole, 226.4 g., of oxo-tridecylvinyl ether (assay, 99.9%) was stirred and swept with nitrogen as it washeated to 72 C. with stirring by a high-torque stirring motor capable ofabout 50-500 r.p.m. and fitted with a blade closely conforming to thebottom of the 1 liter 4-necked flask. The flask was equipped with twoaccurately graduated additional funnels, the larger of which had astopcock with an integral needle value for constant drop rateadjustment, a thermometer, and a condenser closed by a bubble-countingseal containing mineral oil.

When the temperature had been stabilized at 72 C. the addition of awarmed solution of 98.0 g. of maleic anhydride in 150 g. of reagentgrade xylene was begun and continued at a constant rate such that theaddition was completed in 4.5 hours. Initially, 3.0 ml. of a 10.0 ml.benzene solution of 0.51 g. of azobisisobutyronitrile (AIBN) was added;the remaining 7.0 ml. was added in 0.5 ml. portions at 15 minuteintervals over the following 3.5 hours.

During the addition period the temperature was maintained at 72.5 C.i0.5C. with efficient mixing as the viscosity increased. After completion ofthe additions, the viscous solution was stirred and heated, graduallyincreasing the temperature to 75 C. during two hours. A sample of themixture was withdrawn and dried two hours at 130 C.; the resulting drybrittle polymer sample weighed 2.3 g. and was dissolved in methyl ethylketone to give a 1.00% solution. The average specific viscosity of this1% copolymer sample at 25 C. in methyl ethyl ketone, multiplied by 4,was 1.82.

The remaining hot copolymer solution was treated dropwise with heatingand stirring with 267 g. of isobutanol, heated and stirred at 75 C. anadditional three hours, cooled, and diluted with xylene to 1074 g.,giving a 30% (copolymer solids) solutions.

A one molar proportion of a tridecyl vinyl ether/maleic anhydrideisobutanol partial ester prepared as described above is treatedaccording to this invention by adding thereto an excess molar proportionof epichlorohydrin, relative to the equivalent of one mole of carboxylgroup content in the maleic half ester moiety of the polymer, and acatalytic amount of hexadecyltrimethylammonium chloride, stirring untilhomogeneously mixed, and then adding gradually one molar proportion ofsodium methoxide dissolved in excess methanol, while heating the mixtureto reflux. Upon removing distillables there is obtained as product atridecyl vinyl ether/poly(isobuty1 glycidyl) mixed maleate esterpolymer.

EXAMPLE 17 A 1 molar proportion of the tridecyl vinyl ether/poly-(isobutyl glycidyl) mixed maleate ester prepared as described in Example16, is dissolved in a 2:,1 volume proportion mixture of 2-propanol andwater, and then treated slowly with one molar proportion ofN,N,N,'N'-tetramethylethlenediamine, equivalent to the glycidyl contentof the poly(isobutyl glycidyl) mixed ester, with stirring at roomtemperature, and then treated with dilute hydrochloric acid solutionuntil the pH of the mixture is reduced to between about pH 5 to pH 6.

The resulting polyamine polymer may be applied to cellulose pulpslurries to size the resulting paper without any alkaline pre-treatment.

The embodiments of the invention in which an exclusive property orprivilege is claimed are defined as follows:

1. A sized paper product comprising a cellulosic web sized with a sizingamount of a polyamine composition prepared by reacting an aliphaticdiamine with a poly(alkyl glycidyl) mixed maleate ester of a member ofthe group consisting of (a) an adduct of maleic anhydride and anon-conjugated, olefinically unsaturated, non-hydroxylated fatty oilcontaining an average of from to about 24 carbon atoms in the fatty acidmoiety of said oil, and (b) a copolymer of maleic anhydride and apolymerizable alpha-olefin having from 2 to about 4 carbon atoms, in thepresence of an organic hydroxyl containing material which isvolatilizable at temperatures below C., and water, at a temperature offrom about 0 C. to 50 C., and then treating the resulting reactionproduct with an acid to adjust the pH of said reaction product to fromabout 5 to 7.0.

2. A sized paper product as described in claim 1 wherein the po1y(alkylglycidyl) mixed maleate ester is prepared by reacting an epihalohydrinwith a carboxyl group containing lower alkyl partial ester of a memberof the group consisting of (a) an adduct of maleic anhydride and anon-conjugated, olefinically unsaturated, non-hydroxylated fatty oilhaving an average of from 10 to about 24 carbon atoms in the carbonchain of the fatty acid moiety of said fatty oil, and (b) a copolymer ofmaleic anhydride and an alpha-olefin, in the presence of a quaternaryammonium catalytic compound, and an alkali metal salt forming basiccompound at a temperature of from about 50 C. to reflux temperature.

3. A sized paper product as described in claim 2 wherein theepihalohydrin used is epichlorohydrin and partial ester startingmaterial is a partial methyl ester of an adductof maleic anhydride and anon-conjugated, olefinically unsaturated, nonhydroxylated, fatty oilhaving an average of from 10 to about 24 carbon atoms in the carbonchain of the fatty acid moiety of said fatty oil.

4. A sized paper product as described in claim 3 wherein excessepichlorohydrin is reacted with a partial methyl ester of a maleicanhydride adduct of safllower oil.

5. A sized paper product as described in claim 2 wherein theepihalohydrin is epichlorohydrin and it is reacted with a partial alkylester of a copolymer of maleic anhydride and an alpha-olefin.

6. A sized paper product as described in claim 5 wherein epichlorohydrinis reacted with a partial methyl ester of a copolymer of maleicanhydride and an alpha-olefin hydrocarbon.

7. A sized paper product as described in claim 6 wherein excessepichlorohydrin is reacted with a partial methyl ester of a copolymer ofmaleic anhydride and styrene.

8. A sized paper product as described in claim 1 wherein the aliphaticdiamine is an aliphatic amine of the formula wherein R is selected fromthe group consisting of hydrogen and methyl, each R is an alkyl radicalof from 1 to 2 carbon atoms, and R" is a bivalent alkylene radicalhaving from 2 to 6 carbon atoms, and the poly(alkyl glycidyl) mixedester is a poly(methyl glycidyl) mixed maleate ester of a partial methylester of a copolymer of maleic anhydride and an alpha-olefin having from2 to 40 carbon atoms, and the acid used to adjust the pH is a hydrohalicacid.

9. A sized paper product as described in claim 8 wherein N,N,N,N'tetramethyl 1,2 ethylene diamine is reacted with a poly(rnethylglycidyl) mixed ester of a copolymer of maleic anhydride and styrene inthe presence of aqueous methanol, the hydrohalic acid is hydrochloricacid and the pH is adjusted from pH 5 to pH 6.

10. A method of sizing cellulosic containing paper sheet which comprisesadding to the aqueous pulp used to prepare said paper a sizing amount ofan aqueous dispersion of a polyamine composition prepared by reacting analiphatic diamine with a poly(alkyl glycidyl) mixed maleate ester of amember of the group consisting of 15 (a) an adduct of maleic anhydrideand a non-conjugated, olefinically unsaturated, non-hydroxylated fattyoil containing an average of from 10 to about 24 carbon atoms in thefatty acid moiety of said oil, and (b) a copolymer of maleic anhydrideand a polymerizable alpha-olefin having from about 2 to about 40 carbonatoms, in the presence of an organic hydroxyl containing material whichis voiatizable at temperatures below 100 C., and water, at a temperatureof from about 0 C. to 50 C., and then treating the resulting reactionproduct with an acid to adjust the pH of said reaction product to fromabout 5 to 7, and forming a paper sheet from said aqueous pulp.

References Cited UNITED S. LEON BASHORE,

STATES PATENTS Primary Examiner F. FREI, Assistant Examiner

